N hydroxymethylated dialkyl phosphonoalkyl carbamates

ABSTRACT

NOVEL COMPOSITIONS SUITABLE FOR USE AS FLAME RETARDANTS AND HAVING INSECTICIDAL PROPERTIES, N-HYDROXYMETHYLATED DIALKYL PHOSPHONOALKYL CARBAMATES AND N-HYDROXYMETHYLATED DI(HALOALKYL) PHOSPHONO ALKYL CARBAMATES.

United States Patent 3,763,283 N-HYDROXYMETHYLATED DIALKYL PHOSPHONOALKYL CARBAMATES Mark N. Curgan, Greenville, S.C., assignor to C. H. Patrick & Co., Inc., Greenville, S.C.

N Drawing. Filed Oct. 17, 1969, Ser. No. 870,423 Int. Cl. C07f 9/40 US. Cl. 260-938 3 Claims ABSTRACT OF DISCLOSURE Novel compositions suitable for use as flame retardants and having insecticidal properties, N-hydroxymethylated dialkyl phosphonoalkyl carbamates and N-hydroxymethylated di(hal0alkyl) phosphono alkyl carbamates.

This invention relates to a new composition useful as a flame retardant having the formula:

R 0 ll R is alkyl or haloalkyl having 1-4 carbon atoms R is an alkylene group having 2-4 carbon atoms n is l or 2 A new class of compounds of the type, N-hydroxymethylated dialkyl phosphono alkyl carbamates has been synthesized.

where R is alkyl or haloalkyl having l-4 carbon atoms R is an alkylene group having 24 carbon atoms n is 1 or 2 When applied to cellulosic materials, such as cotton, Dacron-cotton blends, paper, rayon or wood, these compounds impart an improved degree of durable flame resistance. These monomers are thought to be reacted with cellulosic fiber and upon application to the fabric and curing impart improved flame resistance. These com pounds are useful in making flame resistant fabric, paper, wooden products, and urethane foams. Fabrics on which the combination is useful include those constructed of natural fibers, synthetic fibers and/ or blends. These compounds also have insecticidal properties.

The N-hydroxymethylated dialkylphosphonoalkyl carbamates can be prepared in a two step process involving the initial reaction of a chloralkyl carbamate with a trialkyl phosphite, to form an intermediate dialkylphosphonoalkyl carbamate, according to the following general reaction:

P-OR ClROCNH:

This intermediated product is then hydroxymethylated by reaction with either one or two mol equivalents of formaldehyde or paraformaldehyde so as to produce the desired hydroxylated dialkylphosphonoalkyl carbamate.

ice,

R is alkyl or haloalkyl having 1-4 carbon atoms R is an alkylene group having 2-4 carbon atoms n is 1 or 2 In further accord with this invention, the hydroxymethylated dialkylphosphonoalkyl carbamates prepared by the above reactions are employed as fiameproofing agents for cellulosic fibrous material by incorporating the product in a finishing composition consisting of an aqueous solution or emulsion containing a thermosetting resin forming compound, at least one of the flame-retardant compounds of the invention, and preferably, an acid producing catalyst such as those commonly used in conjunction with the production of thermosetting resins or with the impregnating of textile materials by thermosetting resin-forming compounds. Such a pad bath also preferably includes a compatible conventional soil release composition. Suitable catalysts, for example, may include ammonium chloride, Z-amino-2-methylpropanoll-hydrochloride, zinc nitrate, magnesium chloride, magnesium fiuoroborate, and the like. Of the thermosetting resin-forming compounds suitable for use in the invention, particularly good results can be achieved using aminoplastic resin-forming compound, such as the 1,3-dimethylol-S-alkyl-perhydrotriazone, urea formaldehyde, melamine-formaldethyde, tetramethylol acetylene diureine, 1,3-dimethylol-4,S-dihydroxy ethyleneurea, etc. Other resin-forming compounds which may be used include acrylates, polyesters, and silicones.

More particularly, the finishing compositions of this invention are generally comprised of from 0 to 15 percent by weight and preferably from about 3 to about 12 percent by weight of the thermosetting resin-forming compound, from 10 to 50 percent by weight and preferably 20 to 40 percent by Weight of the flame retardant compound, from 0.25 percent to 3 percent by weight and preferably from about 0.5 percent to 2.5 percent by weight of said acid producing catalyst, water being the principal remaining constituent of the finishing composition.

The finishing composition may contain other additives, as desired, to achieve additional desired properties. Such additives may consist of softening agents, bodying agents, surface active agents, water repelling agents, etc.

The following is typical of such a finishing composition:

Percent by wt.

Flame retardant compound 40. Thermosetting resin-forming compound 5 Urea 1 Softening agent 0.6 Acid producing catalyst 0.4 Water 53.0

Further examples are as follows:

EXAMPLE I Preparation of Z-(dimethylphosphono) ethyl-l-carbamate 300 g. (2.4 mol) of 2 chlorethyl-l-carbamate, 301 g. (2.4 mol) of trimethyl phosphite, and 5 g. of triethylamine were charged to a 1 liter round bottomed flask equipped EXAMPLE V phonoalkyl carbamates, synthesized as in Examples II Preparation of Z-(diethylphosphono) ethyl-l-carbamate through represented by the following Welghts:

123-6 F f i Y f 2-(diethylphosphono) ethyl-l-carbamate 225.1 IT101) of methyl Phosphlte, and 3 of trlethyla'mll'le 2-(diisopropylphosphono) ethyl-l-carbamate 253.1 were charged to a 500 all round bottom flask, q pp 2-[di-(2-chlorethylphosphono)] ethyl-l-carbamate. 294.1 with thermometer, reflux condenser, and stirrer, and heat- 3-(dimethylphosphono) propyl-l-carbamate 211.1 ed at 140 C., until a weight loss of 64.5 g., equivalent 4-(dimethy1phosph0n0) butyl-l-carbamate 225.1

to one mol of ethyl chloride, was obtained. The residue consisted of Z-diethylphosphono ethyl-l-carbamate. To 8L1 g. (1 mol) of 37% f ld h d Solution, 034

EXAMPLE VI g. of anhydrous dibasic sodium phosphate was added, followed, with stirring, by the slow addition of 1 gram mol Preparation of izfigiggg of the respective carbamate. During this addition, the pH of the solution was held at 7 by the addition, as needed,

123.6 g, (1 mol) of 2-chlorethy1-larbamat 208.2 g. of 10 percent sodium carbonate solution. The end of the (1 mol) of triisopropyl phosphite, and 3 g. of triethylreaction was indicated by no further decrease in the free amine were heated to 150 C., until a loss of weight of formaldehyde content of the solutions. The resulting solu- 78.5 g., equivalent to one mol of isopropyl chloride, was tions contained the respective N- ydroxymethyl dialkylobtained. The residue consisted of 2-(diisopropylphosphonoalkyl carbamates.

phono) ethyl-1-carbamate. 2O

EXAMPLE VII 'EXAMPLE XI Preparation of 2-(di-Z-chlorethylphosphono) ethyl-l- Application of N hydmxymethyl (dialkylphosphono) carbamate alkyl carbamates to fabric for flame retardant purposes 123.6 g. (1 mol) of 2-chlorethyl-l-carbamate. 269.5 g. 5 Pad baths were prepared of the following composition: (1 mol) of tri (2chlorethyl) phosphite, and 5 g. of triethylamine were heated at 150 C., until a loss in weight of 99 g., equivalent to one mol of ethylene dichloride,

Percent by Wt. N-hydroxymethyl (dialkylphosphono) alkyl had occurred. The residue consisted of 2-(di-2-chlorethylcarbamatc 1 2 to 50 phosphono) ethyl-l-carbamate. Aerotex Resin 23, Special 3 5 Urea 1 EXAMPLE VIII Fabritone PE 4 0.6

Ammonium chloride 0.4

Preparation of 3-(dimethylphosphono) propyl-lcarbamate Water q.s. 100.0.

1 The following materials were used N-hydroxymethyLZ-(dimethylphosphono) ethyl-l-carbamate N-hydroxymethyl-2-(diethylphosphono) ethyl-l-carbamate 137.6 g. (1 mol) of 3-chloropropyl-l-carbamate, 124.1 g. (1 mol) of trimethyl phosphite, and 2.2 g. of triethylamine were h t d t 125 C. ntil a lo of 5() 5 g N-l1ydr0xymethyl'2-(diisoprcpylphosphono) ethyl-1-carbamate equivalent to one mol of methylchloride had occurred. ,f},{f,{; phosphono] The residue consisted of 3- dimeth l hos hono ro ly y v p o o) pron -ca b te 1 b t yp p p Py 40 Nhydroxymethy1-4(dimethylphosphono) butyl-l-carbamate ama Since fabrics of difierent construction were treated, the amount of fiameproofer varied to compensate with varying pickup of fabric upon padding, in order that a resulting 40 EXAMPLE IX i n 4. 1 h S h a 15 percent of tiameproofer on wei ht of fabric would occur. Preparat o of (dlmethy P o p butyl 1 carb 6 American Cyanamid Compaiiy (trimethylol melamine).

151.6 g. 1 mol) of 4-chlorbutyl carbamate, 124.1 g. H. Patrick & Co. polyethylene emulsion)- 1 l of tr'meth l hos h'te, and 2.5 .oft i th 1 nc mo) 1 y p p 1 g r e y mm A lightweight white broadcloth and a khaki medium h t d t 135 C., unt'l los f ht f 50.5 were ea e a 1 a s 0 welg o g weight fabric, were treated with the pad bath described equivalent to one mol of methyl chloride had occurred. a The residue consisted of 4 (dimethylphosphono) buty1 above. The fabric was air dried, cured by heating at 350 1- b F. for 1 minute and 40 seconds. After the first and fifth EXAMPLE X laundering, the fabric was conditioned at 70 F. and 65% relative humidity before testing for flame-proofing. The

Preparatlon of g gig dlalkylphosphonoalkyl efiiciency of the treatments was determined by Test Methcar am s od AATCC 34-1966, Fire Resistance of Textile Fabrics. One gram mol, respectively, of each of the dialkylphos- The results of these tests are shown in Table II.

TABLE II.FIRE RESISTANCE OF FABRIC Number of washes Fabric AF A G CL AF A G C L Flarneprooter applied at 40% o.w.f.:

N-hydroXymethy1-2(dimethylphosphono) ethyl-1-carbamate White broadcloth 0 AF=after-fiarne, expressed in seconds.

AG aiterglow, expressed in seconds.

CL=charlength, expressed in inches.

BEL=burned entire length, but skeletal structure of fabric entirely preserved. Burned very slowly. TC=burned entire length, rapidly. Skeletal structure of fabric entirely destroyed.

7 8 What is claimed is: 3. N,N-di(hydroxymethyl) 2 (dimethylphosphono) 1. A composition of matter, N-hydroxymethylated diethyl-l-carbamate. I alkyl phosphono alkyl carbamatc, of the formula: References Cited RO\C|? 1 UNITED STATES PATENTS PR'O cNHHwmomn 5 3,069,312 12/1962 Kohn 260938 X 3,365,530 1/1968 Bahr et a1 260938 X Where LEWIS GO'ITS, Primary Examiner L,

R is alkyl or haloalkyl having 1-4 carbon atoms 10 R L R AYMOND Assistant Examiner R 15 an alkylene group havlng 2-4 carbon atoms n is 1 or 2 US. Cl. X.R.

2. N-hydroxymethyl Z-(dimethylphosphono) ethyl-l- 117*136; N, 459 R, 8 969 carbamate. 

